Organic syntheses via transition metal complexes.: 109.: Transfer of carbene ligands from group VI metals to rhodium as the key step of a rhodium-catalyzed reactivity enhancement of Fischer carbene complexes

被引:37
作者
Göttker-Schnetmann, I [1 ]
Aumann, R [1 ]
机构
[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany
关键词
D O I
10.1021/om0007724
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Vinylcyclopentadienes 5a-h were obtained under mild conditions at 20 degreesC in 71-78% yields by a rhodium-catalyzed condensation of 1-alken-3-ynes 4a,b with 4-amino-1-metalla-1,3-butadienes (OC)(5)M=C(OEt)CH=C(Ph)NR2 (3; M = W, Or). The key step of this transformation involves formation of a rhodaoctatetraene (type B) by transmetalation and a subsequent insertion of the alkyne unit into the Rh=C double bond. RhCl3. 3H(2)O in CH3OH was found to be a simple and most efficient (pre)catalyst of this reaction. [(COD)RhCl](2) and [(OC)(2)RhCl](2) have been also successfully applied as precatalysts.
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页码:346 / 354
页数:9
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